US3133020A - Extreme pressure lubricants - Google Patents
Extreme pressure lubricants Download PDFInfo
- Publication number
- US3133020A US3133020A US70444A US7044460A US3133020A US 3133020 A US3133020 A US 3133020A US 70444 A US70444 A US 70444A US 7044460 A US7044460 A US 7044460A US 3133020 A US3133020 A US 3133020A
- Authority
- US
- United States
- Prior art keywords
- percent
- lithium
- extreme pressure
- greases
- grease
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000314 lubricant Substances 0.000 title description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 239000000344 soap Substances 0.000 claims description 18
- 239000004519 grease Substances 0.000 claims description 14
- 235000011187 glycerol Nutrition 0.000 claims description 10
- 230000001050 lubricating effect Effects 0.000 claims description 8
- -1 LITHIUM FATTY ACID Chemical class 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- KDQZPXCKTHKGQM-UHFFFAOYSA-L bis(dipentylcarbamothioylsulfanyl)lead Chemical compound [Pb+2].CCCCCN(C([S-])=S)CCCCC.CCCCCN(C([S-])=S)CCCCC KDQZPXCKTHKGQM-UHFFFAOYSA-L 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 14
- 150000005846 sugar alcohols Polymers 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000010687 lubricating oil Substances 0.000 description 7
- 239000010688 mineral lubricating oil Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000004359 castor oil Substances 0.000 description 4
- 235000019438 castor oil Nutrition 0.000 description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001647090 Ponca Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229940072106 hydroxystearate Drugs 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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- C—CHEMISTRY; METALLURGY
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
- C10M117/02—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
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- C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
- C10M117/02—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
- C10M117/04—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen containing hydroxy groups
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
- C10M129/06—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/08—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least 2 hydroxy groups
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/30—Polyoxyalkylenes of alkylene oxides containing 3 carbon atoms only
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- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/32—Polyoxyalkylenes of alkylene oxides containing 4 or more carbon atoms
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/104—Aromatic fractions
- C10M2203/1045—Aromatic fractions used as base material
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
- C10M2203/1065—Naphthenic fractions used as base material
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/108—Residual fractions, e.g. bright stocks
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/108—Residual fractions, e.g. bright stocks
- C10M2203/1085—Residual fractions, e.g. bright stocks used as base material
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
- C10M2207/1225—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic used as thickening agent
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- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/124—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof
- C10M2207/1245—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof used as thickening agent
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- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M2207/10—Carboxylix acids; Neutral salts thereof
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- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
- C10M2207/1265—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic used as thickening agent
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- C10M2207/10—Carboxylix acids; Neutral salts thereof
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- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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- C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/16—Naphthenic acids
- C10M2207/166—Naphthenic acids used as thickening agents
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/18—Tall oil acids
- C10M2207/186—Tall oil acids used as thickening agents
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/20—Rosin acids
- C10M2207/206—Rosin acids used as thickening agents
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/24—Epoxidised acids; Ester derivatives thereof
- C10M2207/246—Epoxidised acids; Ester derivatives thereof used as thickening agents
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/106—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
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- C10N2010/06—Groups 3 or 13
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N2010/16—Groups 8, 9, or 10
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
Definitions
- E.P. extreme pressure
- Langner US. Patent No. 2,785,130, discloses extreme pressure lubricants comprising lubricating oils containing a lead soap, polyhydric alcohol, and extreme pressure agent selected from halogenated an sulfohalogenated organic compounds. It is taught in this patent that it is essential to provide an extreme pressure agent containing a portion of a halogenated or sulfo-halogenated organic compound; thus the patentee in this instance derives at extreme pressure properties through the combined use of lead, alcohol, active halogen, and in some instances active sulfur. The patentee further teaches that extreme pressure properties are reduced by use of the alcohol in the absence of active halogen.
- Still another object of this invention is to provide improved lithium soap greases containing small amounts of an aliphatic polyhydric alcohol and a metal organodithiocarbamate.
- Yet another object of this invention is to provide improved lubricating oils having high E.P. properties and containing small amounts of an aliphatic polyhydric alcohol and a metal organodithiocarbamate.
- lithium base lubricating greases comprising a mineral lubricating oil thickened with a lithium soap and having incorporated therein an aliphatic polyhydric alcohol and a metal organodithiocarbamate.
- the invention is directed to lubricating oils containing an aliphatic polyhydric alcohol and a metal organodithiocarbamate.
- the mineral lubricating oils which are employed in the compositions of this invention can be derived from naphthene or paratfin base crude and can be either residual or distillate oil or a mixture thereof, depending on the particular grease or lubricant which is being prepared.
- a blend of a residual oil with a distillate oil has been found particularly suitable in meeting the viscosity requirements for the various grades.
- the lithium base lubricating greases which are well 3,133,028 Patented May 12, 1964 known in the art, comprise a dispersion of a lithium soap in a mineral oil. Usually, a calculated amount of soap, between about 5 percent and about 25 percent or higher by weight, is dispersed in the mineral oil base followed by heating at an elevated temperature, for example, from about 350 to about 450 F. until the mixture thickens. Subsequently the hot grease is cooled to provide the final product. Mixing or milling can be provided as desired during any of the preparation steps.
- Various soaps or admixtures of soaps can be employed in the lithium base greases; however, preferably, the soaps are hydroxy fatty acid soaps of lithium.
- a particularly desirable grease is obtained through the employment of soaps derived from mixtures of a hydroxy fatty acid and a hydrogenated fatty material, for example, hydrogenated fish oil, castor oil, and the like. Further details concerning the latter greases and their method of preparation are set forth in US. Patent 2,475,589.
- polyhydric alcohol and metal organodithiocarbamate which are added to the lubricants of this invention can be incorporated in the grease at any stage in its preparation; however, preferably, these materials are added during the final steps of preparation.
- Any of the aliphatic polyhydric alcohols can be employed in the lubricating compositions, including alcohols containing 2,
- R and R represent hydrogen or organic groupings similar or dissimilar in nature, and present in the molecule so that the sum R +R contains at least eight carbon atoms in alkyl groups, and the structural relationship indicated by the relative positions and linkages of the respective atoms in the formula.
- the organic groupings represented by R and R can be alkyl, aryl, alkylaryl, mixture of alkyl and aryl, cycloalkyl and heterocyclic groupings. These groupings can contain inorganic substituents, such as sulfur, oxygen, phosphorus and nitrogen, when special properties are sought.
- R and R groups when wholly organic, contain a total of at least 8 carbon atoms in alkyl groups.
- Considerable improvement in this regard is effected by increasing the number of carbon atoms in alkyl groups to 10, 12, and 16, preferably.
- the preferred dithiocarbamates are those in which the organo groups are alkyl groups and particularly the lead .dialkyldithiocarbamates, for example, lead diamyldithioferred as stated previously.
- the polyhydric alcohol and the metal organodithiocarbamate provide improvement in ER properties, these materials are ordinarily employed within certain percentage ranges, namely, from about 0.1 to about 5.0 percent by weight of the alcohol based on the grease and preferably from about 0.3 to about 1 percent; and from about 0.4 to about percent of the metal organodithiocarbamate based on the grease and preferably from about 1.0 to about 4 percent.
- the compositions can also contain small amounts of the conventional additives which are incorporaterl for specific purposes, including anticorrosive agents, pour depressants, viscosity improvers, oxidation inhibitors, dyes, and the like.
- the combination of the polyhydric alcohol and metal organodithiocarbamate is found to give substantial improvements in the extreme pressure properties of the lithium soap greases without a corresponding adverse effect on the mechanical stability of the greases and without limitation as to the type of polyhydric alcohol which is employed.
- This combination of additives also provides a similar effect in lubricating oils.
- Example 1 The following is given as an example of a base lubricant composition having extreme pressure properties:
- Example 2 grease prepared by open kettle saponification of a mixture of hydrogenated castor oil and lZ-hydroxy stearic acid in a mineral lubricating oil. Its finished approximate composition was as follows:
- Example 3 Weight Percent Dithio- Timken Test carbamate- OK"Load, Mineral Oil Pounds Mixture Weight Percent Addition Polyhydric Alcohol Added 7 o Ethylene Glycol"- Hexylene Glycol.
- a lithium base lubricating grease consisting essentially of a mineral lubricating oil thickened with lithium fatty acid soap and containing between about 0.1 and.
- a lithium base lubricating grease consisting essentially of a mineral lubricating oil thickened with between about 1 and about 25 percent of the lithium soap of a h droxy fatty acid and hydrogenated castor oil and containing from about 0.1 to about 5.0 percent glycerin and from about 0.4 to about 10.0 percent lead diamyldithiocarbamate.
- a lithium base lubricating grease consisting essentially of a mineral lubricating oil thickened with between about 1 and about 25 percent by Weight of the lithium soap of a hydroxy fatty acid and hydrogenated castor oil hydroxy fatty 5 6 and containing from about 0.3 to about 1.0 percent by 2,504,672 Farrington ct a1 Apr. 18, 1950 weight glycerin and from about 1.0 to about 4.0 per- 2,785,130 Langer Mar. 12, 1957 cent by weight lead diamyldithiocarbamate. 2,794,781 Diamond et a1 June 4, 1957 2,812,306 Liehe Nov. 5, 1957 References Citcfi in the file of this patent 5 2,358,273 Worth Oct.
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- Engineering & Computer Science (AREA)
- Lubricants (AREA)
Description
United States Patent 3,133,026 EXTREME PRESSURE LUBRICANTS William P. Scott, Ponca City, Okla, assignor to Continental Oil (Zompany, Ponce Qity, Okla, a corporation of Delaware No Drawing. Fiied Nov. 21, 1960, Ser. No. 79,444 4 (Claims. (Cl. 252-836) This invention relates to extreme pressure lubricants having improved properties and particularly lubricants adapted for heavy duty service. In one aspect, the invention relates to lubricating oils and in another aspect to lithium base greases.
The prior art discloses numerous additives which are employed to provide E.P. (extreme pressure) properties to lubricating oils and greases. For example, Langner, US. Patent No. 2,785,130, discloses extreme pressure lubricants comprising lubricating oils containing a lead soap, polyhydric alcohol, and extreme pressure agent selected from halogenated an sulfohalogenated organic compounds. It is taught in this patent that it is essential to provide an extreme pressure agent containing a portion of a halogenated or sulfo-halogenated organic compound; thus the patentee in this instance derives at extreme pressure properties through the combined use of lead, alcohol, active halogen, and in some instances active sulfur. The patentee further teaches that extreme pressure properties are reduced by use of the alcohol in the absence of active halogen.
In US. Patent No. 2,858,273, impartation of ER properties to calcium soap greases is provided by incorporating as additives a polyhydric alcohol, a metal organodithiocarbamate, and an alkanol amine. The patentee teaches that the alkanol amine is essential to his greases in order to provide good mechanical stability. He further teaches that only those alcohols containing 3 or 4 hydroxyl groups are operative in his compositions.
The applicant has found that certain specific greases and lubricating oils in general can be considerably improved in E.P. properties by the use of a particular combination of additives not disclosed by the prior art.
It is therefore an object of this invention to provide improved lithium soap greases having high E.P. properties.
It is another object of this invention to provide improved lithium IZ-hydroxy stearate greases having improved E.P. properties.
Still another object of this invention is to provide improved lithium soap greases containing small amounts of an aliphatic polyhydric alcohol and a metal organodithiocarbamate.
Yet another object of this invention is to provide improved lubricating oils having high E.P. properties and containing small amounts of an aliphatic polyhydric alcohol and a metal organodithiocarbamate.
The foregoing objects are realized broadly by providing lithium base lubricating greases comprising a mineral lubricating oil thickened with a lithium soap and having incorporated therein an aliphatic polyhydric alcohol and a metal organodithiocarbamate.
1n one aspect, the invention is directed to lubricating oils containing an aliphatic polyhydric alcohol and a metal organodithiocarbamate.
The mineral lubricating oils which are employed in the compositions of this invention can be derived from naphthene or paratfin base crude and can be either residual or distillate oil or a mixture thereof, depending on the particular grease or lubricant which is being prepared. For example, in an automotive gear lubricant, a blend of a residual oil with a distillate oil has been found particularly suitable in meeting the viscosity requirements for the various grades.
The lithium base lubricating greases, which are well 3,133,028 Patented May 12, 1964 known in the art, comprise a dispersion of a lithium soap in a mineral oil. Usually, a calculated amount of soap, between about 5 percent and about 25 percent or higher by weight, is dispersed in the mineral oil base followed by heating at an elevated temperature, for example, from about 350 to about 450 F. until the mixture thickens. Subsequently the hot grease is cooled to provide the final product. Mixing or milling can be provided as desired during any of the preparation steps. Various soaps or admixtures of soaps can be employed in the lithium base greases; however, preferably, the soaps are hydroxy fatty acid soaps of lithium. A particularly desirable grease is obtained through the employment of soaps derived from mixtures of a hydroxy fatty acid and a hydrogenated fatty material, for example, hydrogenated fish oil, castor oil, and the like. Further details concerning the latter greases and their method of preparation are set forth in US. Patent 2,475,589.
The polyhydric alcohol and metal organodithiocarbamate which are added to the lubricants of this invention can be incorporated in the grease at any stage in its preparation; however, preferably, these materials are added during the final steps of preparation. Any of the aliphatic polyhydric alcohols can be employed in the lubricating compositions, including alcohols containing 2,
in which R and R represent hydrogen or organic groupings similar or dissimilar in nature, and present in the molecule so that the sum R +R contains at least eight carbon atoms in alkyl groups, and the structural relationship indicated by the relative positions and linkages of the respective atoms in the formula. The organic groupings represented by R and R can be alkyl, aryl, alkylaryl, mixture of alkyl and aryl, cycloalkyl and heterocyclic groupings. These groupings can contain inorganic substituents, such as sulfur, oxygen, phosphorus and nitrogen, when special properties are sought. Particularly important to the proper functioning of these compounds is that they possess adequate solubility in the mineral base stock and for this reason it is generally required that the combined R and R groups, when wholly organic, contain a total of at least 8 carbon atoms in alkyl groups. Considerable improvement in this regard is effected by increasing the number of carbon atoms in alkyl groups to 10, 12, and 16, preferably.
The preferred dithiocarbamates are those in which the organo groups are alkyl groups and particularly the lead .dialkyldithiocarbamates, for example, lead diamyldithioferred as stated previously. Although very minor amounts of the polyhydric alcohol and the metal organodithiocarbamate provide improvement in ER properties, these materials are ordinarily employed within certain percentage ranges, namely, from about 0.1 to about 5.0 percent by weight of the alcohol based on the grease and preferably from about 0.3 to about 1 percent; and from about 0.4 to about percent of the metal organodithiocarbamate based on the grease and preferably from about 1.0 to about 4 percent. The compositions can also contain small amounts of the conventional additives which are incorporaterl for specific purposes, including anticorrosive agents, pour depressants, viscosity improvers, oxidation inhibitors, dyes, and the like.
The combination of the polyhydric alcohol and metal organodithiocarbamate is found to give substantial improvements in the extreme pressure properties of the lithium soap greases without a corresponding adverse effect on the mechanical stability of the greases and without limitation as to the type of polyhydric alcohol which is employed. This combination of additives also provides a similar effect in lubricating oils.
The following examples are presented in illustration of the invention:
Example 1 The following is given as an example of a base lubricant composition having extreme pressure properties:
Several blends were prepared in which various polyhydric alcohols were added to the above lubricating base. The following table shows the data obtained:
Weight Tirnken Test Polyhydrlc Alcohol Added Percent 0K Lord,
Addition Pounds None r Glycerin 0. 2 Glycerin 0.3 Ethylene glycol 0. 3 Polypropylene glycol 0.6 Polybutylene glycol 0. 6 Polybutylene glycol 4 0. 6 50 1 The Timken Test was run according to the direction given by the A.S.T.M. Committee D-2 (A.S.T.M. Bulletin No. 181, page 43, April 1952). Special Timken steel blocks N o. T 15349 and Timken cups No. T-48fi5l were used. Ten-minute rims are made at various load levels. These levels are increased until failure occurs which is indicated by obvious scoring of the test specimens. The maximum load without failure and the unit pressures existing at this maximum sale load are considered as the performance criteria.
2 Average molecular weight 1350-1100.
3 Average molecular weight 1,000.
4 Average molecular weight 1,500.
The above data illustrate the effectiveness of the combination of the polyhydr-ic alcohol with a metal organedithiocarbamate, glycerin being particularly effective as the alcohol.
Example 2 grease prepared by open kettle saponification of a mixture of hydrogenated castor oil and lZ-hydroxy stearic acid in a mineral lubricating oil. Its finished approximate composition was as follows:
Percent by weight Lithium soap 5.5 Mineral lubricating oil a 94.5
Weight Percent Dithio- Timken Test carbamate- OK"Load, Mineral Oil Pounds Mixture Weight Percent Addition Polyhydric Alcohol Added 7 o Ethylene Glycol"- Hexylene Glycol The above data illustrate the effectiveness of the com- 7 Example 3 The following data were obtained to illustrate the effect of glycerin on the mechanical stability of lithium greases similar to the base grease employed in Example 2:
BATCHES WITH GLYCERIN ADDED (10,000-POUND BATGHES) A.S.T.M. D 217-52'1 Penetration Grease Batch 'Ilmken 60 Stroke 10,000
Stroke 1 BATCHES WITHOUT GLYCERIN 3 10,000 strokes in five-hole Worker.
1. A lithium base lubricating grease consisting essentially of a mineral lubricating oil thickened with lithium fatty acid soap and containing between about 0.1 and.
about 5.0 percent glycerin and between about 0.4 and about 10.0 percent lead diamyldithiocarbamate.
2. A lithium base lubricating grease consisting essentially of a mineral lubricating oil thickened with between about 1 and about 25 percent of the lithium soap of a h droxy fatty acid and hydrogenated castor oil and containing from about 0.1 to about 5.0 percent glycerin and from about 0.4 to about 10.0 percent lead diamyldithiocarbamate.
3. The grease of claim 4 in which the acid is lZ-hydroxy stearic acid.
4. A lithium base lubricating grease consisting essentially of a mineral lubricating oil thickened with between about 1 and about 25 percent by Weight of the lithium soap of a hydroxy fatty acid and hydrogenated castor oil hydroxy fatty 5 6 and containing from about 0.3 to about 1.0 percent by 2,504,672 Farrington ct a1 Apr. 18, 1950 weight glycerin and from about 1.0 to about 4.0 per- 2,785,130 Langer Mar. 12, 1957 cent by weight lead diamyldithiocarbamate. 2,794,781 Diamond et a1 June 4, 1957 2,812,306 Liehe Nov. 5, 1957 References Citcfi in the file of this patent 5 2,358,273 Worth Oct. 28, 1958 UNITED STATES PATENTS OR PATENTS 2,201,258 B11886 y 21, 1940 50 ,1 7 Canada Sspt, 2 1954 2,400,106 Denison et a1 May 14, 1946 UNITED STATES PATENT OFFICE QETIFICATE OF CURRECTION Patent N00 3 lSS OQO May 12 1964 William P, Scott It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as o orrected below a Column l line 2O for 'an read "--and--- column lline 70 for the claim reference numeral "4' read-s 2 Signed and sealed this 10th day of November 1964::
(SEAL) Attest:
ERNEST W. SWIDER' EDWARD J. BRENNER Attesting Ufficer Commissioner of Patents
Claims (1)
1. A LITHIUM BASE LUBRICATING GREASE CONSISTING ESSENTIALLY OF A MINERAL LUBRICATIN OIL THICKENED WITH LITHIUM FATTY ACID SOAP AND CONTAINING BETWEEN ABOUT 0.1 AND ABOUT 5.0 PERCENT GLYCERIN AND BETWEEN ABOUT 0.4 AND ABOUT 10.0 PERCENT LEAD DIAMYLDITHIOCARBAMATE.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL271605D NL271605A (en) | 1960-11-21 | ||
BE621872D BE621872A (en) | 1960-11-21 | ||
US70444A US3133020A (en) | 1960-11-21 | 1960-11-21 | Extreme pressure lubricants |
GB38258/61A GB949254A (en) | 1960-11-21 | 1961-10-25 | Extreme pressure lubricants |
FR878496A FR1305161A (en) | 1960-11-21 | 1961-11-09 | Lubricants for service under extremely high pressures |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US70444A US3133020A (en) | 1960-11-21 | 1960-11-21 | Extreme pressure lubricants |
Publications (1)
Publication Number | Publication Date |
---|---|
US3133020A true US3133020A (en) | 1964-05-12 |
Family
ID=22095320
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US70444A Expired - Lifetime US3133020A (en) | 1960-11-21 | 1960-11-21 | Extreme pressure lubricants |
Country Status (4)
Country | Link |
---|---|
US (1) | US3133020A (en) |
BE (1) | BE621872A (en) |
GB (1) | GB949254A (en) |
NL (1) | NL271605A (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3248325A (en) * | 1964-08-21 | 1966-04-26 | Phillips Petroleum Co | Lubricating composition |
US3622512A (en) * | 1969-05-06 | 1971-11-23 | Us Air Force | Grease compositions of polyol aliphatic esters |
US3891564A (en) * | 1972-02-14 | 1975-06-24 | Texaco Inc | Process for preparing mixed lithium-calcium soap thickened greases |
US4481125A (en) * | 1982-05-03 | 1984-11-06 | E.F. Houghton & Co. | Water-based hydraulic fluid |
WO1985000182A1 (en) * | 1983-06-29 | 1985-01-17 | E. F. Houghton & Co. | Water-based hydraulic fluid |
US4740322A (en) * | 1985-07-29 | 1988-04-26 | The Lubrizol Corporation | Sulfur-containing compositions, and additive concentrates, lubricating oils, metal working lubricants and asphalt compositions containing same |
FR2619392A1 (en) * | 1987-08-13 | 1989-02-17 | Cofran Rech Sarl | Sulphur-containing additives for lubricants and greases, especially for gears, and lubricants and greases containing them |
US4822505A (en) * | 1987-07-31 | 1989-04-18 | Exxon Research And Engineering Company | Load-carrying grease |
US5916851A (en) * | 1995-12-22 | 1999-06-29 | Japan Energy Corporation | Lubricating oil for internal combustion engine comprising oxymolybdenum dithiocarbamate sulfide |
US20140082986A1 (en) * | 2012-09-21 | 2014-03-27 | Kevin W Gay | Firearm lubricant and methods for using |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2201258A (en) * | 1936-08-11 | 1940-05-21 | Goodrich Co B F | Extreme pressure lubricant |
US2400106A (en) * | 1944-10-16 | 1946-05-14 | California Research Corp | Compounded oil |
US2504672A (en) * | 1948-11-01 | 1950-04-18 | California Research Corp | Lithium grease |
CA506167A (en) * | 1954-09-28 | A. Edgar John | Grease composition | |
US2785130A (en) * | 1953-12-21 | 1957-03-12 | Texas Co | Extreme pressure lubricant |
US2794781A (en) * | 1955-02-25 | 1957-06-04 | Shell Dev | High temperature aromatic-free mineral lubricating oil compositions |
US2812306A (en) * | 1954-06-23 | 1957-11-05 | Standard Oil Co | Lithium soap grease containing rust and copper corrosion inhibitors |
US2858273A (en) * | 1956-05-28 | 1958-10-28 | Union Oil Co | Extreme pressure lubricating grease |
-
0
- BE BE621872D patent/BE621872A/xx unknown
- NL NL271605D patent/NL271605A/xx unknown
-
1960
- 1960-11-21 US US70444A patent/US3133020A/en not_active Expired - Lifetime
-
1961
- 1961-10-25 GB GB38258/61A patent/GB949254A/en not_active Expired
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA506167A (en) * | 1954-09-28 | A. Edgar John | Grease composition | |
US2201258A (en) * | 1936-08-11 | 1940-05-21 | Goodrich Co B F | Extreme pressure lubricant |
US2400106A (en) * | 1944-10-16 | 1946-05-14 | California Research Corp | Compounded oil |
US2504672A (en) * | 1948-11-01 | 1950-04-18 | California Research Corp | Lithium grease |
US2785130A (en) * | 1953-12-21 | 1957-03-12 | Texas Co | Extreme pressure lubricant |
US2812306A (en) * | 1954-06-23 | 1957-11-05 | Standard Oil Co | Lithium soap grease containing rust and copper corrosion inhibitors |
US2794781A (en) * | 1955-02-25 | 1957-06-04 | Shell Dev | High temperature aromatic-free mineral lubricating oil compositions |
US2858273A (en) * | 1956-05-28 | 1958-10-28 | Union Oil Co | Extreme pressure lubricating grease |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3248325A (en) * | 1964-08-21 | 1966-04-26 | Phillips Petroleum Co | Lubricating composition |
US3622512A (en) * | 1969-05-06 | 1971-11-23 | Us Air Force | Grease compositions of polyol aliphatic esters |
US3891564A (en) * | 1972-02-14 | 1975-06-24 | Texaco Inc | Process for preparing mixed lithium-calcium soap thickened greases |
US4481125A (en) * | 1982-05-03 | 1984-11-06 | E.F. Houghton & Co. | Water-based hydraulic fluid |
WO1985000182A1 (en) * | 1983-06-29 | 1985-01-17 | E. F. Houghton & Co. | Water-based hydraulic fluid |
GB2152529A (en) * | 1983-06-29 | 1985-08-07 | Houghton & Co E F | Water-based hydraulic fluid |
US4740322A (en) * | 1985-07-29 | 1988-04-26 | The Lubrizol Corporation | Sulfur-containing compositions, and additive concentrates, lubricating oils, metal working lubricants and asphalt compositions containing same |
US4822505A (en) * | 1987-07-31 | 1989-04-18 | Exxon Research And Engineering Company | Load-carrying grease |
FR2619392A1 (en) * | 1987-08-13 | 1989-02-17 | Cofran Rech Sarl | Sulphur-containing additives for lubricants and greases, especially for gears, and lubricants and greases containing them |
US5916851A (en) * | 1995-12-22 | 1999-06-29 | Japan Energy Corporation | Lubricating oil for internal combustion engine comprising oxymolybdenum dithiocarbamate sulfide |
US20140082986A1 (en) * | 2012-09-21 | 2014-03-27 | Kevin W Gay | Firearm lubricant and methods for using |
Also Published As
Publication number | Publication date |
---|---|
BE621872A (en) | |
GB949254A (en) | 1964-02-12 |
NL271605A (en) |
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